Phonons and structures of tetracene polymorphs at low temperature and high pressure

TL;DR

This study investigates the low-temperature and high-pressure behavior of tetracene polymorphs using Raman spectroscopy and computational modeling, revealing phase transitions and structural details of different polymorphs.

Contribution

It combines experimental Raman spectroscopy with computational structure and phonon calculations to characterize tetracene polymorphs and their phase transitions.

Findings

Identified two tetracene polymorphs with distinct Raman spectra.

Observed pressure-induced phase transition above 1 GPa.

Successfully modeled and matched experimental spectra with computational structures.

Abstract

Crystals of tetracene have been studied by means of lattice phonon Raman spectroscopy as a function of temperature and pressure. Two different phases (polymorphs I and II) have been obtained, depending on sample preparation and history. Polymorph I is the most frequently grown phase, stable at ambient conditions. A pressure induced phase transition, observed above 1 GPa, leads to polymorph II, which is also obtained at temperatures below 140 K. Polymorph II can also be maintained at ambient conditions. We have calculated the crystallographic structures and phonon frequencies as a function of temperature, starting from the configurations of the energy minima found by exploring the potential energy surface of crystalline tetracene. The spectra calculated for the first and second deepest minima match satisfactorily those measured for polymorphs I and II, respectively. All published x-ray structures, once assigned to the appropriate polymorph, are also reproduced.